Resinous composition and process of making same



Patented Dec. 23, 1930 UNITED- STATES PATENrQ;

rnnonoma r. BRADLEY, or wnsrrinnn, NEW JERSEY, Assr'e oB 'ro ELLIS-FOSTER comm, or uo 'rcLAm, NEW JERSEY, A CORPORATION or EW JERSEY v No Drawing. Application. filed June '5,

This invention relates to new -resinouscompositions and process of making the same. These resinous compositions are suitable for use in nitrocellulose coating compositions such as are used for the preparation of artificial leather, automobile lacquers and other typesof lacquers and lacquer enamels having. a nitrocellulose base. These resinous compositions may bemade 1o dride, glycerol and castor oil. Products of .many degrees of hardness may be obtained 7 according to the relative proportion of castor oil employed. Polybasic acids other than phthalic anhydride, such as tartaric, citric,

' malic and maleic acids may be used to wholly or partiall replace the same, polyhydric alcohols ot er than glycerol such as ethyleneand propylene glycols and oils containing hydroxylated atty acids "other than castor oil such as quince oil. In some cases I may also utilize monobasic acids such as benzoic, lactic and similar acids. I may also utilize such natural acidic materials as rosin,

as but in thepreferred. procedure I utilize to best advantage l cerol, phthalic anhydride vand castor oil. g ecastor oil which I preferably employ is known as the Grade AA medicinal quali raw oil, although I may also utilize the lown castor oils, partially h drogenated castor oils, ordinary raw oil- '0 any grade andrefined. or bleached oils. By using a good grade of refined oil I am -able' to produce a lighter colored resin than can be produced with any of the oils mentioned. It is the object of my invention a to produce resins and resinous softeners of lowfacidity, soluble in ethyl and butyl acetates -(or mixtures of these acetates with their corresponding alcohols} and other nitrocellulose solvents, comp etely miscible and compatible with nitrocellulose, both in solution and in the dried film obtained therefrom. In some cases my object also is-to produce resins of extremely light color where-suchcolor is deemed .of value.

In accordance with my invention'a com- .plex resinous substance is formed by reacting simultaneously at an elevated tempera- 'turea mixture; of glycerol, phthalic anhyby chemically combining phthalic anhy-' as to nEsrNous COMPOSITION AND rnocnss or me m 1925. Serial No. 35,264.

dride and castor oil. The reaction is preferably conducted in a suitable container egulpped with a reflux condenser. of such slze "and construction as will tend toeliminate water and other similar Volatile materialwhile at the same time preventing the loss of glycerol and phthalic anhydride. In my pre erred precedureimechanical agitation is employed throughout the reaction. The preferred procedure is to load the kettle with all materials and melt the same, agitation then being employed. The temperature, is then taken slowly to about 290 C. and should never exceed 300 C. Temperatures above 200 C. may in some cases be suflicient to produce. satisfactory resins but where such low temperatures are employed the time taken to complete the reaction-is such eatly increase the cost of the prodnot. other feature is that at temperatures above 230 "C. the castor oil readily enters into combination, whereas at lower temper-- atures the combination is so slow as to at times permit a combination of the phthalic anhydride with the glycerol and formation of an insoluble phthalic glyceride polymer been found to produce darker colored resins Y thanare usually desired. -Tests should be made from time to time until the acid numbefore the castor oil can enter into reaction ber is sufliciently lowered. The batch may then be cooledand the material poured into suitable containers. The acidity of the final product is regulated by the relative amounts of reacting substances employed and by the length of heating and temperature of reaction- In most cases it is advisable to produce a resinous material having an acid number substantially not exceeding 530, since lacquers made from resins of greater acidityhave often been foundto tarnish brass.

Although the relative'proportions of react- 1 mg substances may be varied over a wide range I believe that a definite chemical union of phthalic anhydride, glycerol and castor oil is obtained. This seems evident when it is observed that phthalic anhydride and glycerol when combined alone to form a fusile resin produces a product which is insoluble in ethyl or butyl acetates (or mixtures of these acetates and corresponding alcohols) is relatively high in acidity, the acid number of such material ranging from to 180 and such resin is found to be immiscible with castor oil and nitrocellulose. The reaction product of glycerol phtha'lic anhydride and castor oil or their equivalents are soluble in ethyl and butyl acetates or mixtures of these acetates and'their corresponding alcohols and are of considerably lower acidity, are miscible and compatible with nitrocellulose. Furthermore it should be noted that in certain cases glycerol, phthalic anhydride and castor oil combine to form a resin which when dissolved and incorporated with nitrocellulose does not mix with further quantities (g castor oil aidded in the usualfwaytgs a so ening or p asticizm' g nt or e nitrocellulose, the addition of sl l h castor oil causing the formation of opaque and nonhomogeneous films. If however another type ofsoftener such as diethylphthalate be substituted a clear homogeneous film is obtained.

Thus it will be seen that the castor oil may be chemically combined at relatively high temperatures with the phthalic'anhydride and lycerol but cannot be combined therewith y merely blending cold in solution.

I will now illustrate my invention by describing in detail several specific resmous compositions made by my process and suitable for use in nitrocellulose coatings.

Hard resin A 7 4 parts phthalic anhydride, 45 parts glyc-.

Resin B (resinous softener) 47 parts of lycerol 98 per cent 0. P. 30 parts of phthal i c anhydride, 90 parts of castor 'oil. Tlusresmwasmade'inthesamemanner Soft resin 6' 47 parts glycerol, 98 per cent C. P., 111

parts phthalic anhydride, 140 parts castor oil.

This resin was also made in the same manner as A and produced a rather soft, sticky resin having an acid number of 48.2. This product was freely soluble in ethyl and butyl acetates.

' Many variations in proportions are .permissible according to the nature of the product desired that is the relative degree of hardness, color, solubility and acidity and I therefore do not limit myself to any specific proportions, merely giving the foregoing as illustrative examples.

The many types of resinous compositions which can be produced from these reactions are of great importance to the nitrocellulose coating industries for it now becomes possible to produce materials of from liquid nature to hard and tough solids, all of which are miscible and compatible with nitrocellulose. More of these softer types of compositions than of ordinary castor oil may be admixed with nitrocellulose thus rendering possible the production of more flexible and longer wearing artificial leathers and similar compositions. The elimination of castor oil odors and of rancidifying oils from the artificial leather also constitutes an important advance in the industry.

What I claim is 1. A process which comprises heating a mixture of a polyhydric alcohol, a polybasic carboxylic acid and the glyceride of a hydroxylated fatty acid to a temperature of about 290 C.

2. A process which comprises heating'a mixture of a polyhydric alcohol, a polybasic acid and the glyceride of a hydroxylated fatty acid to a temperature between 230 and 290 v3. A process which comprises heating a mixture of a polyhydric alcohol, a polybasic acid and the glyceride of a .hydroxylated fatty acid to a temperature greater than 200 C., and not above 300 C.

4:. A process which 'heating a mixture of glycerol, phthalic anhydride and castor oil to a temperature of about 290 C.

5. A process which com rises heating a mixture of glycerol, phthahc anhydride and castot-3 to a temperature between 230 and 290 r I 6. A process which. comprises heating a mixture of glycerol, phthalic anhydride and castor oil to a temperature greater than 200 C., and not above 300 C.

7. A process which comprises heating a mixture of a polyhydric alcohol, a polybasic acid, amonobaslc acid and the glyceride of a hydroxylated fatty acid to a temperature of about 290 C.

8. A" process which comprises heating a mixture of a polyhydric alcohol,'a polybasic acid, a monobaslc acid and the glyceride of a hydroxylated fatty acid to a temperature between 230 and 290 C. y w

9. A process which comprises heating a mixture of a polyhydric alcohol, a polybasic acid, a monobasic acid and the glyceride of a hydroxylated fatty acid to a temperature greater than 200 0., and not above 300 C.

10. A process which comprises simultaneously chemically combining a polybasic acid, a polyhydric alcohol and the glyceride of a hydroxylated fatty acid.

11. A process which comprises simultaneously chemically combining phthalic anhydride, glycerol and castor oil.

12. A process which comprises simultaneously chemically combining a polybasic carboxylic acid, a monobasic acid, a polyhydric alcohol and the glyceride of a hydroxylated fatty acid.

13. A process which comprises simultaneously chemically combining phthalic anhy- 14. A resinous softener made by chemically combining a polybasic acid, a polyhydric alcohol and the glyceride of a' hydroxylated fatty acid, the glyceride of the hydroxylated fatty acid being present in excess by weight of the polybasic acid.

15. A resinous softener made by chemically combining castor oil, phthalic anhydride and glycerol, the castor oil being presao ent in excess by weight of the phthalic anhy dride.

16. A resinous softener made by chemicall combinin a polybasic acid, a monobasic aci a polyhy ric alcohol and the glyceride of a hydroxylated fatty acid, the glyceride of the hydroxylated fatty acid being present in excess by weight of the monobasic acid.

17. A resinous softener made b chemically combining castor oil, phtha ic anhydride, benzoic acid and glycerol, the castor oil being present in excess by weight of the phthalic anhydride.

18. A resinous composition made by simultaneously chemically combining a polybasic acid, a polyhydric alcohol and the glyceride of a hydroxylated fatty acid which is light in color, having an acid number not substantially over 30 and which is both miscible and compatible with nitrocellulose.

19. A resinous composition made by simultaneously chemically combining phthalic anhydride, glycerol and castor oil which is light in color, having an acid number. not substantially over 30 and which is both miscible and compatible with nitrocellulose.

20. A resinous composition made by simultaneously chemically combining a polybasic acid, a monobasic acid, a polyhy and a glyceride of a hydroxylated fatty acid having an acid number not substantially over 30 and which is both miscible andcompatible with nitrocellulose;

21. A process as set forth in claim 2 whereu in the mixture is agitated during the reac- Ion.

dride, benzoic acid, glycerol and castor oil.

dllC alcohol a 22. A process as set forth in claim 10 wherein a refined glyceride is utilized.

23. A process as set forth in claim 11 in which blown castor oil is utilized.

24. A resinous reaction product such as that produced by the process of claim 3.

25. A resinous reaction product such as that produced by the process of claim 10.

26. A resinous reaction product such as that produced by the process of claim 11.

27. A resinous reaction product such as that produced by the process of claim 14.

28. A process which comprises heating a mixture of glycerol, phthalic anhydride, rosin and castor oil to a temperature of about 290 C.

29. A process which comprises simultaneously chemically combining phthalic anhydride, glycerol, rosin and castor oil.

30. A resinous softener made by chemically combining castor oil, phthalic anhydride, rosin and glycerol, the castor oil being present in excess by weight of the phthalic anhydride.

31. A resinous composition made by simultaneously chemically combining phthalic anhydride, glycerol, rosin and castor oil having an acid number not substantially over 30 and which is both miscible and compatible with nitrocellulose.

THEODORE F. BRADLEY. 

